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Bronsted-Lowry Acids and Bases

• A Bronsted-Lowry acid is a proton donor.
• A Bronsted-Lowry base is a proton acceptor.
• H+ = proton

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Reactions of Bronsted-Lowry Acids and Bases
•Loss of a proton from an acid forms its conjugate base.
•Gain of a proton by a base forms its conjugate acid.
•A double reaction arrow is used between starting materials and
products to indicate that the reaction can proceed in the forward
and reverse directions. These are equilibrium arrows.

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Lewis Acids and Bases
• A Lewis acid is an electron pair acceptor.
• A Lewis base is an electron pair donor.
• Lewis bases & Bronsted-Lowry bases - both have an available
electron pair—a lone pair or an electron pair in a  bond.
• A Bronsted -Lowry base always donates this electron pair to a
proton, but a Lewis base donates this electron pair to anything
that is electron deficient.

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Lewis Acids
• A Lewis acid must be able to accept an electron pair, but
there are many ways for this to occur.
• All BrØnsted-Lowry acids are also Lewis acids, but the
reverse is not necessarily true.
o Any species that is electron deficient and capable of
accepting an electron pair is also a Lewis acid.

• Examples of Lewis acids are BF3, AlCl3 and CR3+

(carbocations where R = H or alkyls). These compounds
can accept an electron pair because they do not have
filled valence shells of electrons.
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Acidic and Basic Sites on Organic Molecules
Some molecules contain both hydrogen atoms and lone pairs and
thus, can act either as acids or bases, depending on the particular
reaction. An example is the addictive pain reliever morphine.

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Acid Strength and pKa
•The more readily a compound donates a proton, the stronger an
acid it is.
•Acidity is measured by an equilibrium constant

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It is generally more convenient when describing acid strength to use
“pKa” values than Ka values.

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Factors that Determine Acid Strength
 Anything that stabilizes a conjugate base A:¯ makes the starting
acid H—A more acidic.
 Four factors affect the acidity of H—A. These are:
1. Element effects
2. Hybridization effects
3. Inductive effects
4. Resonance effects
 No matter which factor is discussed, the same procedure is always
followed. To compare the acidity of any two acids:
o Always draw the conjugate bases.
o Determine which conjugate base is more stable.
o The more stable the conjugate base,
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Element Effects: Trends in the Periodic Table
Across a row of the periodic table, the acidity of H—A increases as
the electronegativity of A increases.

Positive or negative charge is stabilized when it is spread over a

larger volume.

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• Down a column of the periodic table, the acidity of H—A
increases as the size of A increases.

• Size, and not electronegativity, determines acidity down a

column.

• Although four factors determine the overall acidity of a

particular hydrogen atom, element effects—the identity of A—
is the single most important factor in determining the acidity of
the H—A bond.

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Hybridization Effects
• One of the factor affecting the acidity of H—A is the hybridization
of A.
Let us consider the relative acidities of three different compounds
containing C—H bonds.

• The higher the percent of s-character of the hybrid orbital, the

closer the lone pair is held to the nucleus, and the more stable the
conjugate base.
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Inductive Effects
• An inductive effect is the pull of electron density through 
bonds caused by electronegativity differences in atoms.
In the example below, when we compare the acidities of ethanol
and 2,2,2-trifluoroethanol, we note that the latter is more acidic
than the former.

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• When electron density is pulled away from the negative charge
through  bonds by very electronegative atoms, it is referred to as
an electron withdrawing inductive effect.
• More electronegative atoms stabilize regions of high electron
density by an electron withdrawing inductive effect.
• The more electronegative the atom and the closer it is to the site
of the negative charge, the greater the effect.
• The acidity of H—A increases with the presence of electron
withdrawing groups in A.

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Resonance Effects
• In the example below, when we compare the acidities of ethanol
and acetic acid, we note that the latter is more acidic than the
former.
• When the conjugate bases of the two species are compared, it is
evident that the conjugate base of acetic acid enjoys resonance
stabilization, whereas that of ethanol does not.

• Resonance stabilization accounts for why carboxylic acids are

more acidic than other compounds with O—H bonds—namely
alcohols and phenols.

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Substituted Benzoic Acids
Recall that substituents on a benzene ring either donate or withdraw
electron density, depending on the balance of their inductive and
resonance effects. These same effects also determine the acidity of
substituted benzoic acids.
Electron-donor groups destabilize a conjugate base, making an acid
less acidic—The conjugate base is destabilized because electron
density is being donated to a negatively charged carboxylate anion.

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Electron-withdrawing groups stabilize a conjugate base,
making an acid more acidic. The conjugate base is stabilized
because electron density is removed from the negatively
charged carboxylate anion.

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Substituent Effects on Acidity

COOH COOH COOH COOH COOH

NO2

NO2
OCH3 NO2
p-methoxy benzoic acid m-nitro p-nitro o-nitro

pKa = 4.46 pKa = 4.19 pKa = 3.47 pKa = 3.41 pKa = 2.16

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Substituent Effects on Acidity

Acidic Stength

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Amino Acids

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Intramolecular H-Bonding
p-nitrophenol is more acidic than o-nitrophenonl.
H
O H
O -
O
+
N
O

+
- N
O O

Maleic acid is more acidic than Fumeric acid but fumerate ion is
more acidic than maleate ion.
O O
H H
C C
C C
OH -H+ O
H
C OH -
C O
H C H C

O O
Maleic Acid Maleiate ion
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Basic Strength and pKb
– The stronger the acid, the weaker its conjugate base will be
– An acid with a low pKa will have a weak conjugate base

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Commonly Used Bases in Organic Chemistry
Common strong bases used in organic reactions are more varied in
structure.

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Basicity of Amines:
Relative basicity of amines can be compared in terms of pKa values
for their respective conjugate acids.

The more basic the amine, the higher the pKa of its conjugate acid
will be

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In the gas phase, basicity in the family of methylamines increases
with increasing methyl substitution.

More alkyl substitution results in more stabilization of the

alkylaminium ion.

In aqueous solution, trimethylamine is less basic than dimethyl- or

methylamine
An alkylaminium ion in water is solvated and stabilized by hydrogen
bonding of its hydrogens with water.
The trimethylaminium ion is solvated less well (and therefore
stabilized less) than the dimethylaminium ion, which has two
hydrogen atoms for hydrogen bond.

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Basicity of Amines:

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Basicity of Arylamines
Arylamines are weaker bases than the corresponding non-aromatic
cyclohexylamines

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Basicity of Heterocyclic Amines
Nonaromatic heterocyclic amines have approximately the same
basicity as their acyclic counterparts.

Aromatic heterocyclic amines (in aqueous solution) are much weaker

bases than nonaromatic amines

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Basicity of Amines:

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Amines versus Amides
Amides are much less basic than amines
The pKa of a protonated amide is typically about zero
One reason for this much lower basicity is that the amide is greatly
stabilized by resonance but the protonated amide is not.

A more important reason for the weaker basicity of amides is that

the nitrogen lone pair is delocalized to the carbonyl oxygen.
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